WO2018078484A1 - Method for applying a layer structure by thermodiffusion to a metallic or intermetallic surface - Google Patents

Abstract

The invention relates to a method for producing a layer structure on a metallic surface of a substrate in an open-loop and/or closed-loop controlled reactor, wherein the layer structure is formed on the metallic surface of the substrate by at least one ply or by at least two identical or different plies, wherein the plies follow one another in a periodically recurring sequence and extend parallel or quasi-parallel to the surface of the substrate, wherein the surface of the substrate has at least one metallic layer.

Description

 Method for applying a layer structure by thermal diffusion onto a metallic or intermetallic surface

Technical area

The invention relates to a method for the application of a protective protective layer by a thermal diffusion process. This is used for both substrates and small parts. In the following, for the sake of simplicity, in the description for the parts treated by thermal diffusion, only substrates will be largely discussed. Wherever it is necessary for better understanding, this term is extended accordingly.

However, the underlying thermal diffusion is in principle applicable to all metallic parts, according to the proviso that a specific charge of the reactor, in which a thermal reaction takes place, is driven with associated process parameters, and that added to form a vapor phase in the reactor those elements which, in quantitative and qualitative terms, initiate the underlying thermal diffusion resp. able to implement.

In particular, it is about the application of defined metallic surface protective layers on substrates, which application resp. Implementation by vapor deposition (sublimation) followed by thermal diffusion and conditioning, according to one or more of claims 1 et seq.

The invention also relates in particular to the overall system for the implementation of the thermal diffusion processes and their methods, as well as the formation of the central process for the process reactor and its method. The invention further relates to:

- applications of different protected methods;

- products from these processes;

Use of the products which can be supplied by the thermal diffusion processes.

Technical aspects of the invention

[0006] "Thermal diffusion" or "thermophoresis" refers specifically to the separation (or mass transport) of gases or liquids in a temperature gradient, the larger molecules preferably migrating to sites of lower temperature.

In the case of charged particles, additional thermoelectric effects (Seebeck effect) occur in addition to the actual segregation. This kinetic interaction of particle and heat flux is a microscopic phenomenon that has not yet been clarified by science in all its aspects, which is why a theoretical exposition of this phenomenon is not given here. However, phenomenologically, these superposition phenomena in the context of linear irreversible thermodynamics are described by the occurrence of non-diagonal elements in a transport coefficient matrix.

The transfer to the diffusion of metallic elements in a real solid (eg cast component) in a temperature gradient is not directly possible. It depends strongly on the crystallographic order of structure (ionic bond or covalent bond, metallic bond), density gradients and disorder (grain boundaries, silk scored, pores, etc.). In any case, during thermal diffusion, a temperature / time gradient as the driving force of this process is necessary. The phase system always strives from a high enthalpy state to a low enthalpy state.

[0009] In this coating process, in principle (for example) only metallic zinc is deposited from the vapor phase onto the surface of the substrate.

First practical basics for thermal diffusion were performed by Thomas Graham / Baptist Fourier and the theoretical derivations by Adolf Fick and Albert Einstein in liquids. It turned out that there is a direct relationship between the migration of the molecules in the gradient, the so-called diffusion coefficients:

The diffusion coefficient of the suspended substance thus depends, except on the giantil constant and the absolute temperature, only on the coefficient of friction of the liquid and on the size of the suspended particles.

Consists in a gas mixture, a temperature difference, so enriches the temperature of the lighter component of the substance to the warmer, the heavier at the colder point.

[0013] "Zinc thermo-diffusion" refers to a state-of-the-art process of corrosion protection of the highest quality, in which the surface of the material is thermochemically modified, resulting in an extremely strong (atomic) bond with the support material ensures that on the one hand an excellent long-term corrosion protection arises, and on the other hand, that this results in a change in the properties of the substrate, for example, in terms of ductility, such a substrate then after Thermodiffusion, wherein the two effects here erfindungswesentiich alternatively or cumulatively reach the implementation. Especially the "thermo-diffusion galvanizing" forms an environmentally friendly process that can be performed without chromium compounds.

The coating process takes place in closed chambers and runs at temperatures up to 380 ° C under a defined gas atmosphere, this temperature is not considered to be absolute. In this case, metallic zinc from the vapor phase described above sublimes on the substrate and grows uniformly on the surface of the same. In contrast to conventional anticorrosive processes, the zinc used in "zinc thermo-diffusion" not only lays flat on the surface of the workpiece to be protected, but also penetrates open cavities, fissured surfaces and the eta gate structure in the edge zone. depending on the microstructural morphology, according to the temperature and density gradient, and thus forms a partial zinc / iron alloy.

Optionally, a subsequent, spezieil selected for use additional coating round off the process, and this is to be regarded as optional only in certain cases.

However, the result according to the invention is designed in such a way that a thin and very high-performance corrosion protection layer is formed from the thermodiffusion process, as a result of which further measures, such as "topcoat", are virtually non-imposed.

To round off the disclosure should be emphasized that in a topcoat so it is known to apply a firmly adhering layer of formless fabric on workpieces. These can be individual layers as well as several cohesive layers. Such coatings can be made by chemical, mechanical, thermal, and thermomechanical processes, demonstrating that such Addition with the inventive thermal diffusion process is unable to develop any internal connection.

The zinc thermal diffusion method is particularly suitable for those areas that are confronted with extreme corrosion conditions, and / or the physical properties of the substrate to be selectively targeted, for example, to obtain a ductility property of the workpiece.

It can therefore be concluded that, unlike the conventional corrosion protection method, the zinc used in the zinc thermal diffusion not only, as mentioned above, deposited on the surface of the workpiece to be protected, but the zinc used beyond penetrates into its metal lattice structure in the edge zone, which then forms a true zinc / iron alloy,

In the spirit of rounding off the disclosure, it should be noted that the coating is a major group of manufacturing processes according to DIN 8580 as a name for a group of different manufacturing processes in which a coating material is applied to a workpiece or on a substrate and there a fixed forms adherent layer.

The coating of components is preferably used in the automotive industry and wherever excellent corrosion protection is sought, at best with other functional physical and decorative properties is to be combined, and precisely against this, the thermal diffusion processes proposed here create at least one sustainable alternative technology respectively. to offer.

In summary, the following aspects can be recognized from "Zinc Thermo-Diffusion AA OTech Technical Media, page 3": The edge layer formed by the ZTD process (zinc thermo-diffusion) is also very gieichmässig in the layer thickness and homogeneous in the macrostructure, even with complicated components (eg., With cavities and internal threads). The result is a uniform minimal roughened surface without zinc skin formation. It is achieved a layer hardness of about 52 HRC. As a result, the components thus treated have a very high resistance to wear, which is not achieved with other corrosion protection methods using zinc.

It can be deduced in favor of the invention that the risk of hydrogen embrittlement mainly because of pickling processes and galvanic coating processes from aqueous electrolytes no longer exists. While it is true that the penetration and storage of atomic hydrogen in the metal structure here changes in the ductility (ductility) of the material, which can lead to brittle fracture and so-called stress corrosion cracking and thus to the construction part failure. In the meantime, the danger of hydrogen embrittlement for the machined components can be excluded by the dry-running ZTD process according to the invention, which makes the method particularly suitable for safety-relevant components.

In addition, can be reduced by a thermal diffusion treatment existing oxygen embrittlement or remedy sustainable by the hydrogen is dissolved out of the substrate during the dry heat treatment again.

Another advantage of using the zinc thermo-diffusion of safety-relevant components is the assurance of dimensional tolerances and torques.

In contrast, by the surface coating with conventional methods, the defined tightening torques can change depending on the layer thickness. In addition, the threads of these coated screws or bolts often need be reworked to ensure the required tolerances. However, the applied protective layer is partially destroyed by the mechanical post-processing and the corrosion protection thus deteriorates sustainably.

Since the zinc-thermo-diffusion is a homogeneous and uniform layer structure and no additional layer is applied, but the corrosion protection is introduced into the edge region of the material, no mechanical post-processing is necessary and the defined dimensional tolerances and torques do not change , In addition, in contrast to other layers, there is no settling behavior, which is also of particular importance for safety-relevant components.

State of the art

The following documents have become known in the art:

From EP 164 64 58 A1 discloses a method for the production of press-hardened components, in particular a body component, which consists of a semi-finished product of an uncured, hot-forming steel sheet, wherein the method is characterized by the following process steps: (i) from the Semifinished product is formed by a cold forming process (in particular a drawing process), a component blank; (ii) the component blank is trimmed at the edge to a boundary contour approximately corresponding to the component to be produced; (iii) the clipped component blank is heated and press cured in a heat press; (iv) wherein from the semifinished product by a cold working method (in particular, a drawing method), a component blank is formed; (v) the component blank is trimmed at the edge to a boundary contour approximately corresponding to the component to be produced; (vi) the cut component blank is heated and press-hardened in a heat-molding die; (vii) the press-hardened The component blank is then coated with a corrosion protective layer in a coating step using a the compounding compound.

EP 164 64 58 A1 discloses a method for producing press-hardened components, in particular a body component. From a semi-finished product of an uncured, hot-forming steel sheet, the process is carried out by the following process steps: (i) from the semifinished product, a component blank is formed by a cold-forming process (in particular a drawing process); (ii) the component blank is trimmed at the edge to a boundary contour approximately corresponding to the component to be produced; (iii) the clipped component blank is heated and press cured in a heat forme; (iv) the press-hardened component blank is coated with an anticorrosion layer in a coating step using a thermal diffusion method.

From EP 1 646 459 B2, a method for the production of press-hardened components, in particular a body component, from a semifinished product from an uncured, hot-forming steel sheet, the method is characterized by fol lowing process steps: (i) from the with a semifinished product which has been pasted over a first layer is formed by means of a cold forming method, (in particular drawing method), a component blank; (ii) the component blank is trimmed at the edge to an approximately corresponding edge contour of the component to be produced; (iii) the clipped component blank is heated and press cured in a hot stamping process; (iv) the press-hardened component blank is coated in a coating step with a second corrosion-inhibiting layer.

Moreover, EP 1 646 459 B2 is characterized in that a procedural ren for the production of press-hardened components, (in particular a bodywork building) is proposed, in which the following process steps are performed from a semi-finished product of uncured, hot-forming steel sheet : (i) the semifinished product precoated with a first layer is heated and press-cured in a hot-forming tool; (ii) the press-hardened component blank produced in this way is trimmed at the edge to a component corresponding to the edge contour; (iii) the press-hardened component blank is coated with a second corrosion-inhibiting layer in a coating step, wherein the second layer is applied to the press-hardened component tube by a thermal diffusion process and wherein the second layer is deposited on both the pre-coating and uncoated regions of the component blank becomes.

DE 10 2004 035 049 B4 discloses a process for the coating of

Steel products, in particular also from high-strength steels and with form-heavy profiles, whereby the following process steps are taken as a basis: (i) by heat treatment of the surface-cleaned steel products in a container; (ii) incorporating in the concurrent zinc powder-containing saturation mixture and a heat-stabilizing filler in the form of granules or oaks; (iii) these incorporations are formed of a metal or alloy which does not react with zinc up to a temperature of 350 ° C and has a melting temperature greater than 800 ° C; (iv) holding and cooling; (v) wherein a saturation mixture having a proportion of about 99 to 100% of finely dispersed zinc powder having a particle size of not more than 10 pm and a mass of 3.5 to 3.7 g per 1 m ^{2 of} the total surface of the parts to be coated a coating thickness of about 1 pm is used; (vi) Thermodifusion saturation and holding are carried out at a temperature of 260 ° to 32 ° C, and immediately after cooling, the products are washed and passivated, first in a solution of pH 4 in stages , 5 to 6.0 and then in a solution with a pH of 10.0 to 1 1, 0, in detail: It will be based on the following process steps; (i) by heat treatment of the surface-cleaned steel products in a container; (ii) in the simultaneously containing a zinc powder saturation mixture and a heat stabilizing filler in the form of granules or beads are introduced; (iii) these incorporations are formed of a metal or alloy that does not react with zinc up to a temperature of 350 ° C and has a melting temperature greater than 600 ° C; (iv) holding and cooling; (v) wherein a saturation mixture having a proportion of about 99 to 100% of finely dispersed zinc powder having a particle size of not more than 10 pm and a mass of 3.5 to 3.7 g per 1 m ^{2 of} the total surface of the parts to be coated a coating thickness of about 1 pm is used; (vi) Thermodifusion saturation and holding are conducted at a temperature of 260 ° C to 320 ° C, and immediately after cooling, the products are washed and passivated, first in a solution having a pH of 4.5 to 6.0 and then in a solution with a pH of 10.0 to 1 1, 0.

EP 2 252 719 A1 has disclosed a method for the production of zinc-coated non-ferrous metal components, in particular for the production of corrosion-protected bodies in mixed construction, which is characterized by the following process steps: (i) the coating on the non-ferrous metal components is applied by a zinc diffusion method using a Zn dust mixture at a temperature in the range of 300 ° to 600 ° C to form a zinc diffusion layer. The application of this method relates to a body component, in particular for motor vehicles, in metal-hybrid or composite construction, in which at least one light metal component and a steel component are joined together, wherein the light metal component carries a zinc diffusion layer, which prevents the direct contact between light metal and steel at the joint.

DE 10 2006 019 567 B3 has disclosed a method for producing a molded component from a semifinished product of curable and hot-workable steel sheet, comprising the following steps: (i) heating the semifinished product to oysterization temperature and (ii) press-hardening in a cold tool , Whose deterrence at least partially a martensitic and / or bainitic Setting structure; (iii) and tempering of the formed semi-finished product at temperatures below 400 ° C to form a molded component with increased yield strength and / or elongation at break compared to the cured component, (iv) wherein for the semi-finished product a chromium-molybdenum steel of the compositions 25CrMo4, 34CrMo4, 42CrMo4 , 25CrMoS4, 34CrMoS4 or 42CrMoS4 is selected.

From DE 10 2006 019 567 B3 then specifically shows that the temperature and duration of the annealing are chosen so that the yield strength is increased by at least 20%. Intervall moderate is proposed here, the tempering at a temperature in the range of 300 ° to 400 ° C, respectively. 300 ° to 330 ° C to be done. In detail: The temperature and duration of the tempering are selected so that the yield strength is increased by at least 20%. Intervall moderate is proposed here, the tempering at a temperature in the range of 300 ° to 400 ° C, respectively. 300 ° to 330 ° C to be done.

From EP 2 369 020 A1 a method for the treatment of a metal element for a motor vehicle has become known, with the following process steps: (i) hardening of the metal element; (ii) removing scale prior to pressing the hardened metal element in an ultrasonic liquid containing an aqueous solution with an organic carboxylic acid at a concentration of 0.1-10 vol%; (ii) coating the metal element in a coating process with an anti-corrosion coating.

US Pat. No. 9,089,886 B2 has disclosed methods for treating a metal element for a motor vehicle, with the following process steps: (i) hardening the metal element so as to obtain a press-hardened metal element; (ii) removing scale from the press on the hardened metal element in an ultrasonic liquid and performing an ultrasonic process to obtain a scale-free metal element: (iii) wherein the aqueous solution is an organic carboxylic acid having a concentration of 0.1 to 10 vol.% is; (iv) and the ultrasound process includes ultrasonic frequencies between 18 kHz and 60 kHz; (v) and coating the metal element in a coating process with an anti-corrosion coating; (vi) wherein the ultrasonic frequency is varied / changed during coating with an anti-corrosion coating.

From EP 1 683 892 A1 resp. DE 10 2005 002 706 B4 has disclosed a method for applying a solid metallic coating to a profiled component made of sheet steel, (i) wherein the profiled component is misted in a treatment space with a metal powder and electrostatic deposited metal powder on the surface of the profile component over the entire surface; (ii) followed by a heat treatment of the profile component, in which the coating is formed by a diffusion process between the steel sheet and the metal powder, followed by cooling of the profile component.

Quantitative therefore goes from DE 10 2005 002 706 B4 a method for applying a solid metallic coating on a profile component made of sheet steel, wherein the profile component misted in a treatment room with a zinc or zinc oxide-containing metal powder and the metal powder electrostatically on the Surface of the profile component is deposited over the entire surface, whereupon a heat treatment of the profile component at a temperature between 280 ° and 350 ° C over a period of 0.5 h to 4.0 h is made, in which by a diffusion process between the steel sheet and the metal powder of 5 to 40 pm thick Etsen zinc alloy layers are formed, followed by a cooling of the profile component. In detail: The profile component is misted in a treatment room with a zinc or zinc oxide-containing metal powder and the metal powder electrostatically deposited on the surface of the profile component over the entire surface, followed by a heat treatment of the profile component at a temperature between 280C and 350 ° C over a period of 0.5 h 4.0 h is made in softening by a diffusion process between the steel sheet and the metal powder from 5 to 40 pm thick iron-zinc alloy layers are formed, followed by cooling of the profile component followed. From this document goes Furthermore, this heat treatment comprises a heating phase and a holding phase, and the heating phase extends over a period of 0.5 h to 2 h and the holding phase extends over a period of 0 h to 2 h. The cooling phase of the profile part takes place in a period of less than or equal to 1 h.

DE 10 2005 054 847 B3 discloses the use of a component made of high-strength steel, which has been heat-treated at 320 to 400 degrees Celsius after thermoforming and press hardening, as a structural and / or safety component for a motor vehicle.

EP 2 271 784 B1 has disclosed a method for coating a surface of at least one substrate with zinc, (i) in which the at least one substrate to be coated is heat-treated together with zinc as the coating agent at a temperature between 200 ° and 500 ° C. (ii) wherein before the start of the heat treatment in the reaction space in which the substrate to be coated is heat treated, the oxygen content in the atmosphere contained in the reaction space is set to less than 5% by volume, (iii) and then in the heat treatment is started from the reaction space in the thus-prepared atmosphere, and the heat treatment is carried out in the reaction space; (iv) no gas or oxygen-containing gas is supplied during the heat treatment in the reaction space, or a gas is supplied which has been pretreated is that it contains a maximum oxygen content of 100 ppm.

From DE 10 2009 002 868 A1 resp. EP 2 251 450 A1 discloses a process for the production of layered, parallel to the surface arranged AI rich phases. The finished coating thus has a multilayer structure. To produce this multilayer structure, however, the coating process and subsequent diffusion heat treatment to produce the Fe / aluminides and / or silicides must be repeated several times. A multilayer coating structure with alternating sequence of at least two different layers is thus in the cited state of the art can only be achieved by repeatedly repeating the coating process. The selection of the coating methods and coating materials which are suitable for applying such multilayer coating structures, as well as the possible applications of substrates coated in this way, especially at the joints, are correspondingly limited and the application of the layer structure is comparatively expensive. The delimited layer structure and multiple passes usually lead to increased liability problems and defects. In detail: ⁴ substrate (1) having a metallic surface (2) and a multi-layered layer structure (3) arranged thereon, wherein at least two different layers (4, 5) in successive sequence and parallel to the surface (2) of the substrate (1) are arranged, wherein the layer structure (3) is formed as a diffusion layer, wherein layers (4) of a first, intermetallic phase are formed as a matrix in which layers (5) of at least a second, preferably intermetallic phase are periodically formed , ^{4 2} substrate, wherein the layers (4) of the first intermetallic phase of an aluminum-nickel compound, in particular of Al3Ni and / or ΑΙ3ΝΪ2, exist. ^{4 3} substrate, wherein the layers (5) from the second phase of an aluminum-tungsten or aluminum-molybdenum compound, in particular of Al4W, exist. ^{4 4} substrate, wherein the intermetallic phases of the layers (4) and / or the layers (5) of a ternary compound, in particular an Al-Ni-W compound o- the Al-Ni-Mo compound, or a quaternary compound , in particular Al-Ni-Mo-W exist. Comprises ^{4 5} substrate, said matrix two different layers (4 ', 4 ") of different intermetallic phases, which are arranged at different distances from the substrate (1). ^{4 6} substrate, said second layers (5) substantially equidistant within the matrix or formed within a phase of the matrix. ⁷ substrate according to any one of the preceding claims, characterized in that the matrix or the first layers (4 ', 4 ") have a hardness of about 350 to 1100 HV. ^{4 8} substrate, wherein the layers (4 ', 4 ") from the first phase has a thickness of between 0.05 pm and 3 pm, preferably between 0, 1 pm and 0.8 pm have. ^{4 9} substrate, wherein the layers (5) from the second phase has a hardness of about 800 HV and a thickness between 0.05 pm and 3 pm, preferably between 0, 1 μηη and 0.8 μηι have. ⁴ '"substrate, wherein the surface (2) of the substrate (1) and / or the substrate (1) made of an aluminum alloy or aluminum. ^{4 1 l} substrate, wherein the surface (2) of the substrate (1) and / or the substrate (1) made of a nickel-base alloy having a proportion of tungsten and / or of molybdenum. ^{4 12} substrate, wherein the substrate (1) consists of a steel material. ^{4 13} substrate, on the multi-layered layer structure (3) an aluminum layer is arranged. ^{4 14} substrate, on the substrate (1) and below the multi-layered layer structure (3) is arranged a nickel-tungsten layer or a nickel-molybdenum layer, or a nickel-molybdenum-tungsten ^{layer., 5} procedure for producing a multi-layered layer structure (3) from at least two different layers (4, 5) on a metallic surface (2) of a substrate (1), wherein the layers (4, 5) are arranged in periodically repeated succession and parallel to the surface (2 ) of the substrate ( 1), wherein on the surface (2) of the substrate (1) at least one metallic layer (6) is applied and the coated substrate (1) is subjected to a heat treatment and generates the multi-layered layer structure (3) during the heat treatment by diffusion is, wherein the materials of the metallic layer (6) and the surface (2) of the substrate are coordinated such that are formed by the heat treatment layers (4) of a first, intermetallic phase as a matrix, in which layers (5) at least a second, preferably intermetallic phase are formed periodically.

DE10 2010 021 691 A1 relates to a layer composite of two substrates, which are connected to an adhesion-promoting layer, wherein this adhesion-promoting layer receives a one-dimensional composite structure. This allows for a purely inorganic compound of different materials, as well as a greatly improved compound when using adhesives.

EP 1 595 001 B1 discloses a method of coating a surface with a first material and a second material comprising methods the following steps: (i) placing the first material on the surface; (ii) introducing a precursor for the second material into the interior of the first material simultaneously with or after the step consisting of placing the first material on said surface; (iii) transforming the precursor for the second material introduced into the interior of the first material, introducing the second material such that this second material is formed on the first material to be coated and inside the surface disposed on the surface becomes.

EP 0 787 223 A1 discloses a process for chemical vapor deposition. It is a matter of realizing that preferred tin compounds include branched-chain tetraacyloxytin compounds, e.g. Branched-chain tetraacyloxytin compounds, e.g. Tetra-tert-butoxy tin and tetra-isopropoxy tin can be used.

DE 10 080 457 T5 comprises a process for preparing tungsten nitride, which comprises reacting a tungsten-carbonyl compound with ammonia at a temperature below about 800 ° C.

It is claimed by the detailed appreciation of the documents cited in the prior art that they now rightly form an integral part of this disclosure.

Presentation of the invention

The invention, as characterized in the claims, the object of at least one method, Mittein for operating the process, products thereof, applications of the method or uses of the products of the aforementioned types, by thermal diffusion processes formed corrosion-protective structures on substrates or other parts, soft structures consist of single or multi-layer deposition of metallic and / or intermetallic elements of a vapor phase, in a closed container, also called reactor to perform.

It is based on the assumption that an intermetallic compound (more precisely intermetallic phase) is a homogeneous chemical compound which is formed from two or more metals. In contrast to alloys, such compounds have lattice structures which differ from those of the constituent metals. In their lattice, there is a mixed bond of a metallic bond fraction and lower atomic bonding or ion-binding components, which results in superstructures.

To optimize these processes within the reactor, the large resp. Small parts before and after their treatment in the reactor different quality assurance processes, which will be discussed in more detail below.

Essentially, the following advantages can be achieved by the thermal diffusion according to the invention: a) With the highest inorganic corrosion protection, the corrosion protection strength lasts at least twice longer than is the case, for example, with hot-dip galvanizing or similar methods; b) A strong adhesion bond of the applied layers is ensured, without cracking, delamination (delamination) and fractures, and this over the entire range of the possible layer thicknesses of 1 to 120 μηι; c) If in this description, for practical reasons, a slender diction is referred to as a layer thickness, then never the It is the opinion that other coatings could be understood as well, because the very essence of the thermal diffusion pursued here is that the zinc used, not only affects the surface to be protected, but also this element in the metal structure penetrates the substrate, which then a zinc / iron alloy is formed. d) Due to the thermodiffusion-related metailstrukturbezogene connection no cracking and / or detachment (exfoliation) of this layer take place even under bending, tensile, compressive or shearing stresses of the part, also because a maximized adhesion of the diffused elements has taken place These advantages are noticeable even at high frictional stresses of the base material. These advantages can be observed in particular in connection or structural parts, which is also found in force-transmitting parts (screws, rivets, nuts, etc.). e) When using the thermal diffusion according to the invention, it can be achieved that the measurement tolerances and tightening torques are ensured in the case of safety-relevant components. f) When using the thermal diffusion according to the invention, it can further be achieved that the parts treated therewith experience an increase in their dukility, which the Makes parts "elastic", without significantly adversely affecting the original strength values of these parts for their further use g) Basically, the two results mentioned from the thermal diffusion according to the invention, namely corrosion protection and dukfilicity, are alternative or cumulative within one large layer bandwidth can be achieved alternatively or cumulatively.

Further advantages of the invention can be seen therein: h) It ensures a uniform layer thickness even with complicated geometries over the entire extent of the parts. i) Wear protection, seizure protection, smooth coating are guaranteed. j) By itself, the layers produced by thermal diffusion are well suited to be used when in the aftermath of punctual areas with other coatings, such as organic compounds (paints, vulcanization of parts, etc.) are in demand. However, if a layer created by thermal diffusion should be supplemented with such an additional coating, it should be ensured that the temperatures used for this do not exceed the melting limit of zinc, so that finally no disadvantageous thermal load on the diffused elements results. k) The thermal diffusion according to the invention is free of heavy metals or other toxic substances; only environmentally friendly processes are used; there are no sewage or exhaust air problems; no organic solvents are used; the processes are hydrogen-free.

I) As already briefly tinged above, the inventive thermal diffusion over the conventional coating method for the purpose of corrosion protection, for example by hot-dip galvanizing, the advantage that a much better wear and corrosion resistance can be offered, because, among other things, worked with a relatively low process temperature which makes it possible to treat special parts such as springs etc. without losing their mechanical and physical properties and strengths.

Seen in this way, according to the invention, a method for applying a layer structure by thermal diffusion onto a metallic surface of a substrate is disclosed. Strat in a controlled and / or regulated ("open-loop control processes" / "closed-loop control processes") described reactor, wherein the applied layer structure on the metallic surface of the substrate of at least one layer or at least two identical or The layers are parallel to one another or quasi-parallel to the original surface of the substrate The surface of the substrate directly exposed to the thermal diffusion in turn comprises at least one metallic layer, whereby at least this layer in the reactor is supplied with a heat supply Heat input in the reactor beyond a metallic and / or intermetallic vapor phase injected, via which by thermal diffusion, the generation of the

Layer structure is initiated.

The materials used, which on the one hand form the immediately exposed metallic surface of the substrate and on the other hand the metallic and / or intermetallic layers of the diffused layer structure, are matched to each other, wherein the individual layers by a temporally controlled and / or controlled heat supply process continuous or quasi-continuously formed, and wherein these layers of the same or different metallic and / or intermetallic materials or alloys and have the same or different layer thicknesses.

At least the last applied layer has physical and / or chemical properties which provide maximized corrosion protection. At least the last-applied layer then has a tenacity against bending-induced cracking or delamination, this tenacity being at least equal to or greater than the ductility increase of the parts resulting from the thermal treatment of the substrate.

In the present case, tenacity is understood to mean only the adhesiveness of the applied layer structure, resp. its tenacity against a qualitative Losses with respect to the applied layer (s) in the course of their mechanical and / or chemical stress.

In the case of several existing layer layers formed from different material combinations, monotonous and / or periodically alternating sequences are used.

Thus, in the interest of increasing ductility in the thermally finished substrate, slight physical inflexions can readily be accepted. The ductility is defined as the total plastic deformation, between RP 0.2 and the elongation at break. However, this is not further limiting than the strengths of the underlying material of the substrate, preferably a thermoformed cured structural or safety component, remains high; In contrast, structural and safety components are then available, which maximize drape, which is crucial in many applications.

It has thus surprisingly been found that a substantial increase in the yield strength can be achieved by the inventive method. In particular, in the application of the substrates for body parts, but not only, the concomitant decrease in tensile strength remains irrelevant, because this is known to play only a minor role in the design of the construction due to the use of high quality materials with excess physical material values. The elongation at break decreases only insignificantly by the inventive method, this in the order of a few percentage points. On the other hand, however, there is a clear reduction in the sensitivity to cracking compared to the fracture necking values.

This makes it possible to provide body components, but not only, which still have the predicate "high-strength" in terms of the material used, but behave as ductile as possible, so that they can withstand high crash forces Instead of simply tearing or forming cracks, which would then also affect the structure of the surface coating (see also above under the term "tenacity"), these results could be achieved through in-depth experiments for all structural and structural problems Safety components are confirmed.

When referring to a high strength part, for example, and not by way of limitation, reference is made to a high strength steel whose composition has the following weight percents: carbon (C) 0.18% to 0.3%; Silicon (Si) 0.1% to 0.7%; Manganese (Mn) 1, 0% to 2.5%; Phosphorus (P) maximum 0.025%; Chromium (Cr) to 0.8%; Molybdenum (Mo) to 0.5%; Sulfur (S) maximum 0.01%; Titanium (Ti) 0.02% to 0.05%; Boron (B) 0.002% to 0.005%; Aluminum (AI) 0.01% to 0.06%; Remainder of iron, including impurities caused by stripping, wherein after the heat treatment at 320 ° to 400 ° C a tensile strength Rm of 1200 to 1400 N / mm ² , a yield strength Rpo.a of 950 to 1250 N / mm ² and an elongation As of 6-12 % having,

Not conclusive in this context means that other metals / materials can be used with the same advantages.

The operating temperature for the heat treatment of the substrate in the reactor and for carrying out the thermal diffusion takes place between 200 ° and 500 ° C, preferably between 280 ° -380 ° C. Experiments have shown that thermal operation using the latter range (280 ° -8080 ° C.) gives the best results in terms of maximizing ductility in substrates for use as structural and safety components and in achieving adhesion-secure tenacity conformal application of the layer structure Has.

In addition, further experiments have also shown that in certain metallic layer structures with a value-based heat treatment must be worked outside the latter range to achieve an adhesion-resistant tenancy-compliant layer structure, the experiments have also shown that at higher temperatures above 350 ° -380 ° C, the problem of excessive reduction in tensile strength and hardness in the substrate may occur. By a metallurgical adaptation of the material but these disadvantages can be easily eliminated.

In this connection, it should be emphasized that in the case of two or more layers it is advantageous if the metallic composition of the first layer applied directly to the metallic surface of the substrate is characterized by a maximized metallic adhesion, and that this metallic composition is also adhesive then optimally relative to the subsequent layer, the latter having to provide the best condition for the outer protective layer of the substrate. If these two-sided liability expectations (lower layer compared to upper layer) can not be optimally fulfilled, it is possible to work with intermediate layers, which in turn can be applied in continuous operation within the reactor.

As far as the composition of the layers is concerned, at least one layer of the layer structure should consist of a three-phase metal system, namely Al / Zn / Mg, where Zn as the main reaction partner has a content of 60%, Al 1-39% and Mg Restanz to nearly 100% or even 100%, wherein at least one layer of the layer structure composed of an individual or additional metallic phase system consisting of Ti and / or Sn or at least one layer of the layer structure of an individual or additional metallic phase system of AI3N 12 or A. Ni can be added.

Accordingly, it is also possible to provide processes for the production of zinc-coated non-ferrous metal components (NE metal) (see above in connection with the description of a high-strength steel), which are used in particular for the production. In principle, the coating on non-ferrous building blocks is also suitable for a zinc diffusion method using a Zn dust mixture at a temperature in the range from 300 ° to 600 ° C., preferably from 280 ° -380 ° C. is applied to form a zinc diffusion layer. As a non-ferrous metal, for example, but not exclusively, a light metal alloy based on an Al, Ti, or ivlg alloys is used. The Leichtmetalliegierung has an Ai Gehait above 55 wt .-%.

Subsequently, a phosphating coating can be applied as needed to the Zn thermal diffusion layer. Non-ferrous metal parts can also be copper or copper alloys, as well as Al, Ti, Mg alloys. The bow-shaped non-ferrous metal parts can be further formed after the coating by deep drawing or finished. Hot forming of these non-metallic components is also possible, both before and after the coating, wherein this shaping can be carried out in air or under a protective gas atmosphere,

Characterized in that the light metal component itself carries a zinc diffusion layer, the direct contact between light metal and StahlbauteiSe is prevented at the joints. However, if the friction at these contact points is greater than calculated, Hesse can remedy this, for example, by additionally lacquer coating the joints. In all cases, the light metal and steel components can be joined together by a welding process.

The operating temperature in the reactor for the heat treatment of the substrate and for carrying out the thermal diffusion is, as already stated above, between 200 ° and 500 ° C, preferably between 280 ° and 380 ° C. These operations are over a period of time session of <0.5 h up to 4.0 h. This time- Room session includes a heating phase and a holding phase, wherein the heating phase over a period of 0.5 h to 2 h, and the holding phase over a period of 0 h to 2 h extend.

The two phases can also be operated intertemporarily in a sequential manner, so that a strict two-phase sequence is then no longer in the foreground. The main advantage of such a procedure is that the thermal effect can be more targeted to the substrates as needed.

The subsequent cooling phase of the substrate then takes place in an individually defined period of time, which may be less than or equal to 1 h in one case and greater than 5 h in another case.

The interior of the reactor in which the substrate or substrates are subjected to a heat treatment, and these substrates are supplemented by thermal diffusion with a layer structure, is at an operating temperature between 280 ° and 380 ° C with an initial oxygen content of> 1 vol. % driven, wherein the reactor is operated with an overpressure or with a negative pressure, ie continuously with a slight overpressure, well below 1 .5 bar, preferably between 1, 01 and 1 .5 bar, or continuously with a negative pressure between 1 and 20 mbar.

At least one layer has a layer thickness of 1 to 120 μm, preferably 1 to 20 μm. In the case of several layers, these run regularly with respect to one another, quasi-regular or irregular in the X / Y / Z direction of the substrate. Assuming a vertical section through the surface of the substrates, it can be seen that the layers are flat, jagged or undulating to each other and / or the layers can run over each other, discretely wavy or out of phase with each other. The measurement is made by X-Ray or magnetic (Permascope). The thermal diffusion process within the reactor takes place within a preferably fixed temperature range of 280 ° C to 380 ° C (see above), and this for a period of <30 to 240 min. A typical total cycle time is up to 120 minutes.

Important in this context is the temperature tolerance to be considered during the process, which is at a predetermined holding temperature ± 5 ° to ± 20 ° C.

An important interdependence between the process-related maximum temperature and the extent of loading of the reactor with substrates is that the diffusion temperature must always be created uniformly within the entire reactor space within the shortest possible time. This requires that the provision of the optimal temperature for the thermal diffusion of the way in which the reactor is thermally charged, ie in particular when the heat is supplied indirectly, for example via heating coils, respectively. Heating elements, which partially or completely enclose the reactor. In this context, it is obvious that the wall thickness of the reactor is an essential parameter for the process. Preferably, for the provision of temperature, a semicircular geometry should be used both for the heating elements and for the insulation to optimize this by the distance between the heating elements and the outer surface of the reactor embedded therein.

The effective heating zone must preferably be concentrated on the lower half of the tubular reactor where the substrates and the iron and / or non-ferrous metal powders and granules introduced for the thermal diffusion are concentrated. Therefore, heating elements in the upper part of the reactor should be arranged with care. The heating elements and the insulation should be designed maintenance-optimal, with a simple interchangeability is desirable. An equalization of the temperature prevailing in the reactor is achieved in that the tubular slid reactor rotates during the heating phase according to certain criteria. The direction of rotation and the number of revolutions per unit of time can be programmed according to the reactor parameters. Speeds of 1 - 15 rpm are in normal conditions !! intended.

For the monitoring of the thermal treatment of the reactor is equipped with various temperature sensors, which are arranged both on the outer wall and in the interior of the reactor. These sensors monitor the temperature and transmit the measured values to a central control unit, which controls and controls the overall operation of the reactor and thus the entire system.

Typically, the heating of the reactor is divided into three phases (Heizzykien):

^" At step 1 is a fast heating at maximum power after a calculated heating ramp to target temperature within a calculated time,

• In step 2, a heating is provided at a reduced power of the predicted heat retention temperature (within the heat retention temperature tolerance) with the aim of approaching the calculated time as much as possible.

• Step 3 is to ensure maintenance of the predefined temperature throughout the operation.

In general, the reactor can be operated on the basis of firing profiles, according to the following criteria: The controller operates with stored control profiles which can be retrieved upon entering the operation of the reactor to be carried out in operative connection with the operation of the furnace;

The controller operates with free-acting control profiles which continuously or adaptively adapt to the operation of the reactor in operative connection with the furnace based on sensor-acquired information;

The controller has control profiles which are coupled with predetermined control functions;

- The control has a control profile that intervenes predictively.

The controller for the operation of the reactor simultaneously intervenes on the operation of the furnace, wherein the two units are in close thermal operative connection to each other.

The main control of the reactor resp. interdependent with the whole system of the system is programmed to at least the following inputs and outputs, which are in operative connection with the control professionals and regulated:

Production order, project grater, project number; Sequence number of the order; Material of the substrates; Type of substrates; Weight of the substrates; Volume of the substrates; Recipe for thermal diffusion; Type of parts (bulk parts, manual parts or rack parts); Type of load, combined or individual, where combined means that parts, granules and powders are ready premixed for loading; Weight of parts per reactor; Maximaie Thickness dimension of the parts (also input of different dimensions); Number of parts (each type) per reactor; Total mass of parts (calculated from up to 20 different parts); Total mass of racks that support the parts, assuming that they are metallic parts is); The total mass of the introduced granules; Total powder mass of material used for thermal diffusion: Heat retention temperature, heat retention time: Allowable heat retention temperature tolerance; Time required to start up until the target temperature corresponds; Time required for the run within step 1 (see above); Time required for the run within step 2 (see above); Enter the maximum operative temperature for steps 1, 2 and 3 (see above); Date and time of the run Start and run stop: Total cycle time between run start and run stop; Energy consumption for the heating circuit (in kWh); Energy consumption for the cooling cycle (in kWh); Initial parameters for the operation of the other stations of the system, for example related to the reactor, its speed, inclination angle, etc.

The control of the reactor must be programmable so that all necessary process data and processes are stored as control profiles for the various reactor processes and for the interdependent aggregates of the system, in particular the furnace, or can be detected continuously. These control profiles are identified and can be retrieved in a targeted manner, whereby the software is designed so that already when entering the various parameters continuously applicable, possible, probable, predictive control profiles are shown resp. can be offered.

The display of the temperature curve must be electronically recorded and charted during the entire heating process. Preferably, this visibility is designed so that all measurement zones are displayed at the same time. The curve data is continuously saved in Microsoft Excel compatible format. The reactor must be configured so that the process parameters can be saved for quality assurance.

[0087] All zones within the container should have a target holding temperature of preferably 280 ° to 380 ° C. with a temperature tolerance of ± 5 ° to ± 20 ° C. sen. Therefore, according to the current state of knowledge, it is readily responsible to limit the heating elements to a maximum temperature of 650 ° C. The heating elements are preferably divided into 3 zones: a first zone 1 extends approximately to a first third of the tubular reactor; a second zone 2 covers the central portion of the tubular reactor; in turn, a third zone 3 covers approximately the last third of the tubular reactor. However, this breakdown and the routes outlined here are to be understood as qualitative data only.

Ideally, the product-related temperatures over all three zones are kept within a tolerance of at least ± 20 degrees; Preferably, this temperature tolerance should be maintained over all zones during the heating phase. This procedure ensures a uniform temperature even in those cases where uneven product-related loading of the zones is present, i. if some zones have more mass or parts of different thicknesses are present within the zones.

It is therefore necessary to prevent uneven heating within the reactor by the described specifications, because the zones with more mass or thicker parts require a corresponding individual thermal treatment to equalize the process temperature over the entire reactor.

Sonach, the exact measurement of the surface temperature of the tank-shaped reactor and the temperature of the individual product parts in the three zones is essential for the inventive method.

The tubular reactor is placed during the heating and cooling phases in a support car that is designed so that the reactor can freely rotate freely therein. This rotation is maintained as needed during loading and unloading. This support car with the aktor is designed in such a way that insertion into a subsequent process unit can easily take place, with heating and / or subsequent cooling taking place under process-optimized processes in this process unit.

Accordingly, the structure of this process unit (heating / cooling) must be designed and have an infrastructure that can be removed from the operation in the process unit, the heated air from the heating of the reactor air; On the other hand, the processing unit has an infrastructure, which ensures that after completion of the thermal diffusion method, a first cooling of the reactor can use according to predetermined parameters, before the reactor is then transferred to the cooling device provided for this purpose.

Both the removal of the heated air and the supply of the air flow required for cooling should preferably take place over a plurality of locally arranged inlets / outlets around the reactor. In order to reduce the cooling of the reactor from a process temperature of 380 ° C to at least 50 ° C for a certain period of time (see above), a corresponding air blower output must be provided. Ambient air can normally be used for this purpose. Otherwise, the introduction of cooled air should be provided.

Accordingly, it can be said that the course of the thermal processes within the reactor take place continuously regularly, uniformly / nonuniformly, predictively, on the basis of constantly elevated process values and parameters within the reactor.

Before being heat-treated in the reactor, the substrate generally, but not necessarily, passes through the following process steps:

(i) By cold working, a substrate blank is formed; (ii) the substrate blank is cut edgewise to its final or approximately final contour of the substrate;

(iii) The cut substrate blank is subjected to a thermal process and press-hardened in a hot-forming tool. Or:

(i) purification of the starting blank;

(ii) the starting crude is subjected to a thermal process and press-hardened in a hot-to-mold mold;

(iii) The press-hardened starting blank is cut to the final edge contour of the substrate. The substrate is then cooled in the reactor after its heat treatment and coating, cleaned, and annealed at 150 ° -250 ° C for 0.5-2 h.

In general, the main stations of the plant which define the process processes can be summarized as follows; a) Optional: Station for cleaning the surface of the substrates resp. Products (the actual thermal diffusion process begins with b) b) Station for loading the substrates resp. Products in a preferably tubular reactor. c) station (furnace) for performing the thermal diffusion, with the addition of a thermal energy acting on the reactor,

Make a targeted cooling of the reactor. e) transfer of the reactor to an unloading station, f) Subsequently carrying out a cleaning, for example Ultraschallailresni- tion, and passivation of the substrates, respectively. Products in at least one station. f) recycling the thermally conductive filler and / or the saturating mixture from the preceding process and initiating the same in b),

The invention further relates to an application of the method, which is directed to the production of components, in particular structure and safety components, whose use requires a high corrosion protection capability and a high Dukfiiität. These components are made of hot or kaitumform ble blanks, and are preferably intended for means of transport to the road, to train, to air, to water. Road transport means are preferably motor vehicles in which such structural and safety components are advantageously incorporated, and it is only to meet the strict crash standards. These products are preferably high-strength steel (iron metal) or aluminum (non-metal) components which, as stated above, are used in particular in motor vehicles.

Short description of the drawing

The invention will be explained in more detail below with reference to the figures of the drawing. All elements not essential to the instant understanding of the invention have been omitted. The same elements are provided in the various figures with the same reference numerals.

[0099] In the drawing:

Figure 1 is an integral overall view of a plant; Figure 2 is a plan view of the system of Figure 1;

Figure 3 shows the structure of a processing unit in the removal of heat from the. Reactor;

FIG. 4 shows the construction of the heating elements for the provision of the thermal potential, ie the thermal treatment, for the reactor, wherein these heating elements 150 are designed as heating coils;

Figure 5 is a typical zoning within the tubular reactor;

Figure 6 is a three-dimensional view of a typical tubular container operated as a reactor.

Figure 7 is a graph of stress / strain of a thermo-diffusion treated part;

FIG. 8 shows a reactor station before it is loaded;

FIG. 9 shows an operation during loading of the reactor;

Figure 10 shows another operation in loading the reactor;

FIG. 11 shows the Verschiiessoperation a reactor,

FIG. 12 shows an oven in use;

FIG. 13 shows a menu via the retrievable processes; Figure 14 Recipe input option to achieve changes or. Adjustment possibilities of various process parameters;

FIG. 15 shows a control display for monitoring the processes;

FIG. 16 shows a cooling state for the reactors after the thermal diffusion process;

Figure 17 A first stage for discharging the reactor; Figure 18 Another stage for unloading the reactor; FIG. 19 shows a further insertion of the reactor.

Embodiments of the invention

In the following description of the figures, the tubular container in which the physical and chemical reactions concerning the underlying thermal diffusion take place is followed up with the denomination "reactor".

FIG. 1 shows an integral view of a plant 100 which, by definition, forms the prerequisite for carrying out a process for producing a layer structure on a metallic or intermetallic surface of at least one mechanically bonded part in a controlled and / or controlled reactor.

Essentially, the plant 100 is composed of the following main stations; Ä. Station for cleaning the surface of the parts to be treated,

B, station for loading the parts to be treated into a preferably tubular reactor while providing the auxiliary elements which are complementary for carrying out the thermal diffusion.

C, station for carrying out the thermal diffusion in an oven, with the inclusion of the reactor, in which heating takes place by heating the contents thereof.

D, undertaking a targeted cooling of the reactor in a cooling device designed for this purpose.

E, transfer of the reactor to an unloading station.,

F, Subsequent washing and passivation of the treated parts within at least one station designed for this purpose.

G, recycling the thermally conductive filler and / or saturating mixture from the previous process and introducing them into B.

[01 03] The main thermal component of this plant is represented by a heating / cooling unit 1 1 0 (see above C / D), which is shown in heating or preheating operation. The thermal diffusion process takes place in a reactor 120. This reactor is in the form of a tubular barrel which fits into a heatable support car 130. The support car is designed so that the tubular reactor can freely rotate freely therein. This rotation is advantageously maintained during loading and unloading. This support cart with the inserted reactor has means which initially divide the heating of the tubular reactor, the support cart 130 being designed to that it by inserting into a subsequent process unit 140, in which the effective heating takes place. After completion of the thermal diffusion process, at least one preliminary cooling of the tubular reactor may take place in this unit before it is transported further to the cooling apparatus. With the thermal diffusion process, those process-oriented thermally conducted processes take place in the tubular reactor, in which the treated parts are provided with a protective layer according to the regulations.

The heating elements 150 (see Figures 2 and 4) in the support carriage 130 for the supply of heat are located opposite the reactor, preferably at the lower half (see Figure 4), where on the one hand the substrates or other parts due to the rotation of the reactor lower, unless the reactor is so full that at least the substrates behave immovably within the reactor, which is why in terms of heat only on the introduced elements for the thermal diffusion (iron and / or non-ferrous metal powder, granules, etc.). ) Must be considered.

Therefore, heating elements in the upper portion of the reactor are to be arranged only with care. As explained above, such heating elements may at most be arranged integrally around the reactor if uniform heating of all substrates within the reactor can not take place due to the mere heating on the underside. The heating elements and the insulation must also be designed for optimum maintenance, and it is desirable to have a simple interchangeability.

An equalization of the temperature prevailing in the reactor can be achieved by rotating the reactor according to certain criteria during the heating process. The direction of rotation and the number of revolutions per unit of time can be programmed accordingly. Experiments have shown good results when operated at a mean filling of the reactor at a speed of 1 -1 5 U / min. Also, non-uniform resp. Provide non-uniform rotations of the reactor. For the monitoring of the thermal treatment within the reactor this is equipped with various temperature sensors, which are arranged both on the outer wall and in the interior of the reactor. These sensors monitor the temperature profiles and transmit the measured values to a central control unit, which takes over the control and regulation of the overall operation of the system, and thus also the heat supply for the heating of the reactor.

In general, the furnace is operated on the basis of control profiles which operate according to the following criteria: a) the control operates with stored control profiles, which are called up upon input of the operation of the furnace to be carried out; b) The controller has a control profile which is coupled to predetermined control functions; c) The controller has control profiles which intervene predictively; d) The controller operates with free-acting control profile, which adapt continuously or adaptively based on the information collected by sensors for the operation of the furnace;

The control for the operation of the furnace simultaneously detects the operation of the reactor, wherein both units are in close thermal operative connection to each other.

[01 10] Typically, the reactor heating cycle, in particular with a defined thermal diffusion, is divided into three phases: ^• In step 1, a fast heat-up at maximum power to a calculated ramp to target temperature for a calculated time is provided.

^• In step 2, heating is provided at a reduced power of the predefined holding temperature (within the holding temperature tolerance), with the aim of approaching the calculated time.

^• Step 3 is to ensure the maintenance of the predefined temperature throughout the operation.

The thermal diffusion process inside the reactor takes place within a preferably fixed temperature range of 280 ° to 380 ° C, and this for a period of <30 to at least 240 min. A typical total cycle time is at least or less than 90 minutes. Important in this context is the temperature tolerance to be considered during the process, which must have a tolerance range of at least ± 5 ° to ± 20 ° C at a predetermined holding temperature.

[01 12] An important interdependence between the process-related

Maximum temperature and extent of loading of the reactor with substrates or other parts is that the diffusion temperature must always be reached within a very short time. This requires that the provision of the optimal temperature for the thermal diffusion strong of the way in which the reactor is thermally operated, ie in particular in those cases in which the thermal treatment is carried out indirectly, for example via heating coils or. Heating elements which surround the reactor to a certain degree. In this context, it is obvious that the wall thickness of the reactor is an essential parameter for the thermal treatment. Preferably, for the provision of temperature, a semicircular geometry should be used both for the architecture of the heating elements and for the insulation to optimize this by the distance between the heating elements and the outer surface of the reactor (see Figure 4). As already mentioned, at most those cases are excluded from this basic pattern, if by bulky substrates a full (plump) loading of the reactor should be present.

[01 14] The layer structure to be achieved on the surface of the parts by thermal diffusion is formed from at least one layer or from at least two identical or different layers. The layers follow one another and they run parallel or quasi-parallel to the surface of the part or to a preceding layer. At least the surfaces of the parts placed in the reactor have to be supplied with a heat supply, wherein this heat supply is not only introduced from the outside, but also inside the reactor, ie directly, can be provided. This heat supply also acts on the metallic and / or intermetallic materials and / or alloys, which form a vapor phase within the reactor, which then by thermodiffusion the generation of the

Layer structure initiates or accomplished at the part to be treated.

[01 15] If the layer structure is characterized by several layers, at least two of the successive layers are formed by a controlled and / or regulated heat supply in continuous or quasi-continuous mode, these layers being made of identical or different metallic and / or intermetallic materials and / or alloys and have the same or different layer thicknesses. At least the last-applied layer has physical and / or chemical properties which maximize corrosion protection on the treated part, and wherein at least the last-applied layer structure has physical values against bending cracking or exfoliation, which values are at least equal to or greater than the resulting ductility increase the thermal treatment of the parts are. [01 16] Furthermore, the system according to FIG. 1 also has the following complementary aggregates:

[01 17] First of all, a carousel 160 supplemented with devices can be seen, which functions as a charging station and at the same time also serves as a loading station. Here takes place the filling and emptying of the tubular container, ie the reactor 120, with parts instead, which is then brought into position, said container having those infrastructure to later fulfill the function of a reactor can. The carousel forms the basis for receiving the support carriage 130 with the tubular reactor 120 placed therein. Other trailer layouts not shown in detail, for example cranes or robots, can be provided as complementary aids.

[01 18] To the left thereof, ie upstream of the carousel 160, acts a Veriadeeinrichtung 170 shown here in summary, which carries out the loading of the reactor 120 with substrates and / or parts. For a more detailed explanation of the entire loading process, reference is made to FIGS. 9-1.

[01 19] In operative connection with the heat / cooling unit (see also FIG. 12), ie of the actual furnace 110, a complementary assembly 180 is present, which consists of the following subaggregates:

From a vibration device 181 and a separator 182, which make the separation of granules and powder, for example, from AL granules, fillers and powder residues. These subaggregates 181/182 ensure that the separation of the "spent" AL granules, fillers and powder remnants takes place efficiently, but it is advantageous to provide and, if necessary, to provide for at least one further separation operation of the above-mentioned elements Separation these now "spent" elements are transferred to separate containers. However, recycling is possible. Furthermore, there is a vacuum extractor 183, which performs the industrial dedusting of dust and smoke from the operational units. For this purpose, two hoods or caps 184, 185 are used, which on the one hand are self-supporting and are movable by hand for correct positioning. The extractor must be designed for efficient dust extraction of used zinc dust or other thermodiffusion elements used. As a guideline for proper dust extraction, the amount of 10 kg of dust per container applies.

In this context, it is important for safety guards to ensure that there are no local sources of ignition which could come into contact with the dust extraction.

Furthermore, FIG. 1 shows the flow-carrying lines, namely: a) position 101 as a connecting line between the vibration device 181 and the vacuum suction device 183; b) position 102 as a connecting line between the separator 182 and the vacuum aspirator 183; c) position 103 is a first conduit associated with a first cap 184 connected to the vacuum aspirator 183; d) position 104 a second to a second cap 85 belonging line, white ^¬ che is connected to the vacuum suction 183. FIG. 2 shows a top view of the system 100 according to FIG. 1. Here, the heating elements 150 are particularly clearly visible. Another physical view of these heating elements is shown in FIG. The positions attached here are in concordance with Figure 1 and have the final purpose to bring the individual aggregates holistically closer.

In accordance with FIG. 3, the structure of this processing unit 140 must be designed and have an infrastructure such that the air heated from the heating of the reactor can be removed in the named process unit. On the other hand, the processing unit 140 has an infrastructure which ensures that, after the end of the thermal diffusion process, targeted cooling of the reactor can be used according to predetermined parameters before the reactor is transported to a cooling device (see FIG. 16). Both the removal of the heated air and the supply of the air flow required for cooling should preferably take place via a plurality of inlets / outlets around the reactor. To reduce the cooling of the reactor from a process temperature of, for example, 350 ° C to 50 ° C for a certain period of time (see above), a corresponding air blower power must be provided. Ambient air can normally be used for this purpose. Otherwise, the introduction of a cooled air should be provided.

Figure 3 is thus shown as a side view of the system 100 of Figure 1, and it shows in the foreground the processing unit 140 during the cooling of the tubular container, ie the reactor 120. To the cooling process in cooperation with the addition of the cap 185 more efficient To design, the process unit 140 is extended by a cover 141, which ensures that the provided cooling, the reactor 120 as possible integrally detect. Once the reactor has been finished cooled in operative connection with the cooling device according to FIG. 16, the material is then emptied. Figure 4 shows the heating elements 150 for providing the thermal potential for the reactor 120, said heating elements 150 are formed as heating coils, which are an integral part of the support carriage 130. Further, here is one of a plurality of wheels 131, the soft ensure operational rotation of the reactor 120 during heat transfer. Thus, a proper thermal treatment of the contents of the reactor 120 is ensured. If the reactor 120 is loaded with a bulk material consisting of pieces of Kieinteiien, the rotational movements can be provided intermittently or direction-changing, so that these small parts can be treated thermally gieichmässig.

FIG. 5 shows how a typical zone partition is formed within the tubular reactor 120 shown as a sectional view. The aim is to achieve a target holding temperature of preferably 280 ° to 350 ° C with a temperature tolerance of at least ± 5 ° to ± 20 ° C. In these aspects, the heating elements (see Figure 2, Item 1 50 or Figure 4) must be designed for temperatures up to 850 ° C or above.

These heating elements are preferably divided into 3 zones: a first zone 1 extends approximately to a first third of the tubular reactor; a second zone 2 covers the central section of the reactor; in turn, a third zone 3 covers approximately the last third of the reactor. However, this breakdown, as well as the zones and stretches used here, are to be understood as qualitative data only. The typical structure of a reactor is shown in FIG.

[01 30] However, the elements 128 and 129, which are not shown in more detail in FIG.

Element 128 is a thermocouple; the element 129 is a handle which controls the transport and positioning of the reactor 120. FIG. 6 shows, in a three-dimensional view, a typical tubular container 120 which can be operated as a reactor. Essentially, the structure of such a reactor consists of the following complementary elements:

[0132] A head-side flange (end face) 121, a cover (cover) 122, a number of support-like rings 123, an outer rear cover 124, an attachment tube 125, an inner rear cover 126, a recess 127 for receiving a thermocouple ( see FIG. 5). To protect the latter thermocouple 127, the connection pipe 125 is provided with a thermal insulation not shown in detail. A typical length of the tubular container is about 2 m. Other sizing is also possible and preferable on a case-by-case basis.

FIG. 7 shows a graph of stress / strain of a thermally treated part. It contains 3 states:

Pos. 1 ~ delivery condition;

Pos. 2 = At 310 ° C;

Pos. 3 = At 320 ° C.

In terms of the final strain values, the differences in the three states 1 -3 are not dramatic in absolute terms, but in relation to the ductility desired for this purpose according to the invention, these values are significant.

In this context, the critical stress intensity factor Ki _c is referred to a mathematical calculation. The fracture toughness of the claimed layer structure assumes the following values at room temperature:

For steel 50 ± 20 MPaVm

For aluminum alloys 36 ± 10 MPaVm

For aluminum 14-28 ± 5 MPaVm, wherein the critical stress intensity factor Kic is calculated according to the following relationship:

K _ie = σ · _v 7i ^"' ;: · Y

and it means:

δ = the applied voltage:

a _c = the critical crack length (corresponds to half the crack width a = c / 2);

Y = the geometry factor takes into account two properties: First, the stress intensity factor is theoretically only for infinitely large plates regardless of the dimensions of the test specimen; On the other hand, it should be taken into account that no stresses can occur at the crack ends perpendicular to the surface, so that a plane state of stress sets in. This ensures, for example, that at a transverse contraction number of v = 0.3, the plastically deformed zone at the ends is six times wider than in the middle of the sample.

A significant thermodiffusion process is described in the following description of the figures below, namely, from the loading of the reactor, over its heat treatment, to the discharge / reload of the reactor:

[0136] The loading station of the reactor is operated as follows:

Using the example of a component to be treated with the dimension of 0160 x 450 mm and a weight of 55 kg, the loading is carried out as follows:

The process of thermal diffusion takes place in a container, hereinafter referred to as the reactor (see also FIG. 6), in which the components of the thermodiffusion process (for example: 250 kg aluminum granules, 7 kg zinc powder mixture and 4 components) Process are supplied. Depending on the production order, a suitable reactor from the "reactor stand list" is selected, based on: a) material of the parts to be treated (metals or light metals); b) Purified and dried amount of aluminum granules

For this purpose, reference is made by way of example to FIG. 8, from which the available reactors 120 can be seen. From this it can be seen that the type of loading and the amount of loading of the individual reactors can be kept very variable and production-related as required.

As can be seen from FIG. 9, the reactor 120 is placed on the horizontally oriented loading station 201 and subsequently tilted 202 downwards in rotation mode 202 so that the granules can slide backwards in order to simplify the filling process.

As the next step, the reactor 120 is opened, as shown in FIG. For this purpose, the lid 122 fastened with screws (see FIG. 11 when closing) is loosened and deposited by means of a striking screwdriver (see FIG. 11). If the reactor 120 is empty and in use, it is filled with the predetermined and purified amount of aluminum granules.

As is to be symbolized in FIG. 10, in the loading step, the parts to be processed are loaded into the reactor, either as bulk material or with a rack. If a rack is provided, the parts must be evenly secured in it. The distance between the attached parts should not be less than 3 cm. In the example project, the 4 fingers are loosely placed in series on the granulate bed. Each batch can be added to a standard reference part, which then the process over layer thickness and hardness value can be checked and used as a reference part. Finally, the predetermined amount of zinc mixture is added. As is apparent from Figure 1 1, the end face of lid 122 and reactor 121 is first cleaned with a brush for air and dust-tight Verschiiessen the reactor 120 and the seal checked for damage. Close the lid and insert and screw in all grease-lubricated screws 203. The screws are tightened crosswise with the impact driver 204 in a proven manner. Other closure mechanisms are also possible, for example, that the lid with respect to the reactor with a bayonet, Stufenschloss, etc., is provided.

After completion of the closure of the reactor 120, it is moved to the horizontal position and allowed to rotate for 3 to 5 minutes so that the charge can be evenly distributed within the reactor.

Subsequently, the reactor 20 is transported by crane for thermal treatment 50/30 and positioned in the carriage 130.

2. The oven is operated as follows;

FIG. 12 shows an overall view of the operating furnace 110 in which the support carriage / carriage 130 including the reactor 120 (see FIG. 3) has retracted.

To start the process, the furnace control must be assigned a recipe (process parameter) depending on the loading state of the reactor (weight, surface, material). There are two ways to assign the recipe:

- Direct adoption of a stored recipe, as Figure 13 symbolizes

Edit recipe or change recipe, as Figure 14 wants to symbolize IB2017 / 056422

 49

For a recipe composition, the procedure is as follows;

The recipe can be composed of up to six segments (steps) with six parameters each, and can be supplemented with an additional four setting options.

Column 1 [Segment] gives information about the number of segments or process steps,

Column 2 [Ramp / Jump] regulates for each segment the hurry control either via a ramp function or via a jump function:

* A ramp function is a function of the temperature reached at a certain time, and it automatically controls the heating power of the stove until it reaches the set temperature.

* In the case of a jump function, the stove heats up to the setpoint temperature with the specified heat output.

Column 3 [Set Point TC] defines the soli temperature for the segment.

Column 4 [Time Rate] defines the duration until the soli temperature is reached.

Columns 5-7 [TC1 -TC3] define the maximum temperature (heating power) of the heating elements,

[0147] The following is the recipe for a sample project:

The control is basically controlled in comparison with the temperature and the time.

The high protection [guard high] and guard low [guard low] indications in FIG. 14 serve to continuously check whether the desired temperature is within the required bandwidth.

[01 50] If, for example! in the first segment, a temperature value of 100 ° C is desired, and a 5 ° C depth protection is set, the regulation does not allow the system to change to the second segment until the temperature of the reactor has reached 95 ° C. However, if a depth protection of 10 ° C is chosen, the change to the second segment would occur when reaching 90 ° C,

[01 51] The high protection occurs in the same way, but during the lowering of the temperature. But for their application, the use of high protection can mean a significant increase in processing time.

As far as the reactor rotation is concerned, the following applies:

By changing the drive parameter, the rotation of the reactor itself can be set arbitrarily, the usual revolution is between 1 and 15 U / min. However, higher or lower values can be set at any time as required.

After completion of the recipe input, the oven is started via the control unit. [01 54] Carriage with reactor is automatically moved into the oven, furnace roof! lowers, heating process and Reaktorroiation are started. A temperature control element is automatically introduced into the reactor as soon as the lid of the oven (see Figure 12) is closed.

[0155] At the end of the program, all these operations are reversed,

15, the number of the formulation, the temperatures TC1 -TC3 (heating power), the formulation time and the temperature of the temperature control thermocouple are displayed in the reactor 120 during the process.

3. The refrigeration operation is operated as follows:

The actual radiator system, see FIG. 18, has a capacity for five or more reactors, of which two are in the waiting position and the remaining in the cooling zone. Such a radiator system is operated and driven in automatic mode.

In the cooler 300 itself, there are five positions where the reactor 120 to be cooled can be positioned:

The first position is formed by the charging station 301 on the outside.

Second, third and fourth positions are located in the interior 302 of the radiator 300,

The fifth position is the unspecified discharge station outside,

Each time after 90 minutes, using corresponding values for the values, the reactor is automatically moved from one position to the next free one. The Abkühivorgang takes at a 90 minute cycle therefore a maximum of 380 million in total. The minute cycle can be changed in the cooler display as needed. For practical reasons, the reactor temperature is measured in the fourth position (last position before the container is removed from the cooler). Meanwhile, an integral temperature measurement over all positions can be provided. Once the container has cooled to 50 ° C, the cooling process can also be interrupted manually.

4. The unloading is carried out as follows:

After thermodiffusion and after cooling the reactor, its contents, namely aluminum granules, zinc powder mixture and the thermally diffused components, are discharged at the discharge station. For information purposes, reference is made to FIG. 17, which shows, among other things, the hoods or caps 184, 185, the latter being only partially apparent.

After the cooling process, the reactor is placed by crane on the horizontally oriented unloading station and then tilted down during rotation, so that the granules can slide backwards. After that, all screws are loosened with the aid of the impact wrench and placed in the container provided for this purpose.

Before opening the lid, it is essential that the dust extraction be switched on and place it over the opening of the reactor. The lid is removed and stored.

As can be seen from FIG. 18, the reactor is emptied above the sorting plant. From time to time, the reactor is repeatedly raised slightly during the rotation until it is completely emptied. The machined parts, the granules and the remaining zinc powder are automatically separated. When unloading, the rotational speed of the reactor and the vibration intensity of the sorting system must be adjusted. During sorting, the regular on the side of the sorting system should Before unloading the entire reactor, a workpiece is removed in advance, cleaned and controlled with the mobile Permascope the resulting from the thermal diffusion process Zn layer thickness.

As can be seen from FIG. 19, the reactor is filled again with the collected granules after it has been emptied. For this purpose, the granule funnel 303 is lifted by means of a stacker and positioned at the insertion so that the reactor is still free to rotate.

The reactor is allowed to rotate at the highest level and the locking mechanism of the funnel is released. With a plastic hammer, it is easy to knock on the underside of the funnel so that all the granules can flow out into the reactor.

Subsequently, the reactor 120 is closed again according to proven manner. The lid is then properly screwed again. The contents are distributed by rotation within the reactor gieichmässig, whereupon the reactor is ready in the waiting room for the next process run.

Finally, the document "reactor standlist" is updated according to the process of FIG. 8.

Reference numeral! Sste plant

Connecting pipe between 181 and 182 Connecting pipe between 182 and 183 Connecting pipe between 184 and 183 Connecting pipe between 185 and 183 Cooling / heating unit, furnace

reactor

Face of the flange

Cover, lid

Support-type rings

Rear closure cover

connecting pipe

inner rear closure cover

Recording a thermocouple

thermocouple

handles

Support car, carriage

bikes

process aggregate

heating elements

Carousel, loading / unloading station

Complementary assembly

vibration device

separator

2 subaggregates

Vacuum aspirator

Hood, cap

Hood, cap loading

Rotation mode tilted screws

Screwdrivers

cooler

First charging station

Third or fourth charging station granule funnel

Claims

Claims 1. A method of applying a layered structure to a metallic or intermetallic surface of at least one mechanically stressed or susceptible to corrosion component in a plant (100), said plant having at least one control profile controlled and / or controlled reactor (120), which is designed to receive a loading of parts, wherein the layer structure on the surface of the part of at least one layer or at least two identical or different layers is formed, wherein the layers follow one another, parallel or quasi-parallel to the surface of the part or to Run a preceding layer, wherein at least the surface of the placed in the reactor part with a supplied amount of heat is applied, and this amount of heat from the inside and / or externally applied to the reactor, said amount of heat within the reactor in Wirkverbindun g injected with metallic and / or intermetallic elements or alloys added a vapor phase forming reaction, which initiates vapor phase by thermodiffusion formation of the layer structure, wherein at least two of the successive layers, the layer structure by a controlled and / or controlled supply of heat in the process continuous or quasi-process continuous mode are formed, these layers of the same or different metallic and / or intermetallic coating compositions or alloys and have the same or different layer thicknesses, at least the last applied layer of the layer structure has physical and / or chemical properties, which at the part form a maximized corrosion protection, and wherein at least the last applied layer of the layer structure has physical values against bending-related cracking and / or detachment, W at least equal to or greater than the ductility increase of the part resulting from the thermal treatment.

2. The method according to claim 1, characterized in that the individual layers are formed process-continuing by a time-controlled and / or regulated supply of the heat quantity.

3. The method according to claim 1, characterized in that the treated by the thermal diffusion part consists of substrates or Kleinteiien.

4. The method according to any one of claims 1 -3, characterized in that the substrates or small parts made of a ferrous metal and / or a non-ferrous metal.

5. The method according to claim 1, characterized in that the loaded reactor with an internal temperature between 200 ^" and 500 ° C, preferably operates between 280 ° and 380 ° C, wherein the oxygen content of the atmosphere contained in the reactor to less than or equal to 0 Voi .-%, preferably to less than / equal to 5% by volume.

6. The method according to claim 5, characterized in that during the heat treatment in the reactor optionally only a gas is supplied, which is pretreated so that it contains an oxygen content of not more than 100 ppm.

7. The method according to any one of claims 1 -6, characterized in that when a plurality of applied layers a monotonous or periodically alternating sequence of the layers is based. 8, Method according to one or more of claims 1 -7, characterized in that at least one layer of the layer structure of a coating means of a metallic and / or intermetallic single-, two- or multi-phase system is formed.

8. The method according to one or more of the preceding claims,

 characterized in that at least one layer of the layer structure of a coating agent of zinc, a zinc-dust mixture, a zinc / iron alloy is formed.

10, Method according to one or more of the preceding claims,

 characterized in that at least one layer of the layer structure is made of a coating agent of a metallic three-phase system of Al / Zn / Mg, wherein Zn has as main reaction partner a portion of 60%, AS a proportion of 1-39%, and Mg then the balance 100% or nearly 100%,

1 1, Method according to one or more of the preceding claims,

 characterized in that at least one layer of the layer structure consists of at least one coating agent with an additional metallic phase system, at least Ti and / or Sn,

12, Method according to one or more of the preceding claims,

 characterized in that at least one layer of the layer structure consists of at least one coating agent with an additional metallic phase system, at least of AI3N 12 or AisNi. 3, Method according to one or more of the preceding claims,

characterized in that at least one layer consists of at least one intermetallic phase sys- tem.

14. The method according to one or more of the preceding claims, characterized in that the phase systems for forming the layers of the layer structure during the supply of the amount of heat are supplemented directly or indirectly with at least one heat-stabilizing filler.

15. The method according to one or more of the preceding claims,

 characterized in that in a continuous layer structure intermediate layers are formed, which are applied under continuous process heat supply and consist of an adhesive material with respect to the adjacent layers,

16. The method according to one or more of the preceding claims,

 characterized in that the thermal diffusion process in the reactor within a specified temperature range between 200 ° and 500 ° C, preferably between 280 ° and 380 ° C, takes place, with a total cycle time of between <30 to at least 240 min.

17. The method according to claim 16, characterized in that the total cycle time is 90 ± at least 30 minutes in both directions.

18. The method according to claim 16, characterized in that the temperature tolerance during the entire Prozessveriaufs or within the individual steps of the process and against a predetermined Haitetemperatur is at least ± 5 ° to ± 20 ° C.

1 9. The method according to one or more of the preceding claims,

characterized in that the conditional for the thermal diffusion process absolute or scaled supply of the amount of heat for the reactor in relation to the scope and nature of the loading parts.

20. The method according to claim 16, characterized in that the total cycle time include a heating phase and a holding phase, wherein the heating phase over a period of at least 0.5 h to 2 h and the holding phase over a period of at least 0 h to 2 h extend.

21. The method according to claim 20, characterized in that the two phases, heating phase and Haitephase, intertemporarily follow regularly or irregularly stepped on each other.

22. The method according to claim 21, characterized in that the subsequent cooling phase of the substrate takes place during a period of less than, equal to or greater than 1 h.

23. The method according to one or more of the preceding claims, characterized in that at least one layer has a layer thickness of at least one coating agent of 1 -120 pm, preferably 1 -20 pm.

24. The method according to one or more of the preceding claims,

 characterized in that the layers extend with each other regularly, quasi-regularly or irregularly in the X / Y / Z direction of the substrate.

A method according to claim 24, characterized in that the layers, when presented by a vertical cut through the surface of the substrates, are flat, jagged or undulating with respect to each other.

26. The method according to one or more of the preceding claims,

characterized in that the substrate or the substrates in the interior of the reactor are subjected to a heat treatment, and that the substrate or the substrates obtained by thermal diffusion of a layer structure, wherein in the interior of the reactor at an operating temperature between 200 ° and 500 ° C, preferably between 280 ° and 380 ° C, with an initial oxygen content of> 1 vol.% Procedure. , Method according to one or more of the preceding claims,

 characterized in that the substrate essentially undergoes the following process steps prior to its heat treatment in the reactor:

 (i) Cold forming is used to form a substrate blank;

 (ii) The substrate blank is cut edgewise to the final or approximately final contour of the substrate;

 (Iii) The cut substrate blank is subjected to a thermal process and press-cured in a hot-forming tool.

 or

 (iv) the starting blank is subjected to a thermal process and press hardened in a hot forming tool;

 (v) The press-hardened starting blank is cut to the final edge contour of the substrate. , Method according to one or more of the preceding claims,

 characterized in that the Kieinteile undergo at least the following process steps:

 a) optional cleaning of the original parts;

 b) subjecting the piezores to a thermal process in the reactor to obtain a layered structure by thermal diffusion;

 c) Cleaning of the small parts. , Method according to one or more of the preceding claims,

characterized in that the substrate is cooled after the heat treatment and coating in the reactor, cleaned, and annealed at at least 150 ° - 25Q ° C for at least 0.5 - 2 h. 30 Plant for carrying out the method according to one or more of the preceding claims, characterized in that the plant (100) consists essentially of a loading station for the reactor (120), an oven (1 10) for providing the heat supply for carrying out the thermal diffusion process in the reactor (120), a designed for the cooling of the reactor station (300) after completed thermodiffusion process, a discharge station.

31. Installation according to claim 30, characterized in that upstream of the loading station, a station for cleaning the thermodiffusion process can be fed upstream parts.

32. Plant according to claim 30, characterized in that after the discharge station, the parts treated by the thermal diffusion process pass through a washing operafion and passivation.

33. Plant according to claim 30, characterized in that, after the discharge station, a recycling process takes place concerning the elements accompanying the thermal diffusion process.

34. A method of operating the plant according to one or more of claims 30-33, characterized in that the reactor (120) is loaded within the loading station with a number to be treated by the thermal diffusion parts, wherein each complementary amount of aluminum granules and zinc powder mixture added becomes.

35. Method for operating the installation according to one or more of claims 30-33 and 34, characterized in that the following weights are used as the basis for the operation of a process cycle at the loading station of the reactor:

Weight of the large parts to be treated: 220 Kg ± 50 Kg; Weight of Aiuminium Granules: 250 Kg ± 250 Kg;

 Weight of zinc powder mixture: 7 Kg ± 5 Kg.

36 <Method for operating the plant according to claim 30 and / or according to one of claims 31 to 33, characterized in that the furnace (1 10) is operated by a controller, according to the following criteria:

 The controller operates with stored control profiles which are retrieved upon entering the operation of the furnace to be performed;

 The controller operates with free-acting control profiles which continuously or adaptively adapt to the operation of the furnace based on sensor-acquired information;

 -The controller has control profiles which are coupled with predetermined control functions;

 -The controller has control profiles that prädiktsv intervene;

37. A method of operating a plant according to claim 36, characterized in that the control of the furnace simultaneously detects the operation of the reactor.

38. Plant according to claim 30, characterized in that the reactor (120) consists of at least the following elements: a head-side flange (121), a cover (122), a number of support-like rings (123), an outer, rear closing cover ( 124), a connecting tube (125), an inner, rear closing cover (126), a recess (127) for receiving at least one thermocouple (128), at least one handle (129).

39. Plant according to claim 38, characterized in that the Anschiussrohr (125) to protect the thermocouple (128) is provided with a thermal insulation.

40. A method for grinding a reactor according to one of claims 38, 39, characterized in that the thermal diffusion process is based on at least the following process steps:

 a) At step 1, rapid heating at maximum power is initiated at a calculated ramp to solite temperature for a calculated time;

 b) at step 2, heating is provided at a reduced power of the predefined keep warm temperature within the hold temperature toe, with the aim of approaching the calculated time; c) Step 3 is to ensure maintenance of the predefined temperature throughout the operation. 1, method for operating a reactor according to any one of claims 38, 39, characterized in that the thermal diffusion process within the reactor (120) is operated at least by the following control profiles:

 a) On the basis of at least the production order, the project series, the run number of the contract, the material of the substrates or small parts, the type of substrates or Kieinteile, the weight and mass of the substrates or Kieinteile, the volume resp. the total surface of the substrates or small parts, a recipe for the thermal diffusion is given by at least one stored Steuerprofii, which refers to the amount and weight of the underlying elements for the thermal diffusion elements; b) heat-setting temperature;

 c) heat retention time;

 d) permitted tolerance of the heat retention temperature;

e) Time required for start-up until the drawing temperature corresponds; f) time required to pass within a fast heat-up at maximum power to a calculated ramp to solite temperature for a calculated time; g) time required to pass within a heating at a reduced power of the predefined heating temperature within the holding temperature tolerance with the aim of approaching the calculated time;

h) Enter the maximum operating temperature for the following processes:

 At step 1, rapid heating at maximum power is initiated at a calculated ramp to target temperature for a calculated time; At step 2, heating is provided at a reduced power of the predetermined hold temperature within the keep warm temperature tolerance, with the aim of approaching the calculated time; Step 3 is to ensure maintenance of the predefined temperature throughout the operation;

i) date and time of the race, start and run stops;

j) Total cycle time between run, start and run stop:

k) energy consumption for the heating circuit (in kWh);

 I) Energy consumption for the cooling cycle (in kWh);

m) initial parameters for the operation of the other stations of the system, preferably at least with respect to the reactor, its speed, inclination angle.

A method of operating a reactor according to any one of claims 38, 39, characterized in that the reactor (120) is operated by a controller according to the following criteria:

 - The controller operates with stored control profiles which are retrieved when entering the operation of the reactor to be performed;

The controller operates with free-acting control profiles, which continuously or adaptively adapt to the operation of the reactor based on the sensor-acquired information;

 - The controller has control profiles, which are coupled with predetermined control functions;

The control has control profiles which intervene predictively , A method of operating a reactor according to claim 42, characterized in that the control of the reactor gieichzeitig detects the operation of the furnace. A method of operating a reactor according to any one of claims 38, 39, characterized in that the reactor is operated with an overpressure or with a negative pressure, method of operating a reactor according to claim 44, characterized in that the reactor is continuously pressurized between 1, 01 and 1, 5 bar is operated. , A method of operating a reactor according to claim 44, characterized in that the reactor is operated continuously with a negative pressure between 1 and 20 mbar. Process for operating a reactor according to one of Claims 38, 39, characterized in that the course of the thermal processes within the reactor proceeds continuously, uniformly / nonuniformly, predictively, on the basis of continuously elevated process values and parameters within the reactor. Application of the method according to one or more of claims 1 -29, 34-37, 40-47, for the treatment of parts by thermal diffusion, in particular of structural components, safety parts whose use requires a strong corrosion protection and a high Dukiiiität.

49. Application of the method according to claim 48, characterized in that the structural and security parts are made of hot or cold formable blanks, which are intended for means of transport to road, to train, to air, to water.

50. Application of the method according to claim 49, characterized in that in the means of transport to road are motor vehicles.

51. Products produced using the method according to one or more of claims 1-29, 34-37, 40-47, characterized in that the products are high-strength steel or Al components which are preferably used for Motor vehicles are determined.

Products made using one or more of claims 30-33 and one or more of claims 38, 39, and by application of one or more of claims 1-29, 34-37, 40-47, characterized in that the products are metals or non-metals or high-strength steel construction or aluminum construction, which are preferably intended for motor vehicles, installations, process plants, trains, ships, aircraft, rockets, platforms, wind turbines, pipelines, power plants.